EP0467136B1 - Cliché photopolymérisable pour l'impression flexographique - Google Patents

Cliché photopolymérisable pour l'impression flexographique Download PDF

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Publication number
EP0467136B1
EP0467136B1 EP91110805A EP91110805A EP0467136B1 EP 0467136 B1 EP0467136 B1 EP 0467136B1 EP 91110805 A EP91110805 A EP 91110805A EP 91110805 A EP91110805 A EP 91110805A EP 0467136 B1 EP0467136 B1 EP 0467136B1
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EP
European Patent Office
Prior art keywords
layer
photopolymerizable
elastomeric
polystyrene
elastomeric layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91110805A
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German (de)
English (en)
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EP0467136A1 (fr
Inventor
Werner Dr. Abele
Wilfried Schumacher
Manfred Dr. Schober
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont de Nemours Deutschland GmbH
EIDP Inc
Original Assignee
DuPont de Nemours Deutschland GmbH
EI Du Pont de Nemours and Co
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Publication date
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Publication of EP0467136A1 publication Critical patent/EP0467136A1/fr
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Publication of EP0467136B1 publication Critical patent/EP0467136B1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the invention relates to photopolymerizable printing plates, the essential components of which are a photopolymerizable layer and an elastomeric layer applied to this layer, the elastomeric layer containing as a binder at least one polystyrene-containing block copolymer according to the characterizing part of claim 1.
  • Such printing plates are characterized by more cost-effective production and easier and faster processing.
  • Such photopolymerizable printing plates are usually composed of a layer support, if appropriate an adhesive or other underlayer, a photopolymerizable layer which contains at least one polymeric binder, at least one ethylenically unsaturated monomer which is additionally polymerizable by actinic radiation and a photoinitiator or a photoinitiator system, and a cover layer together.
  • a flexible, tear-resistant polymer film is usually located between the photopolymerizable layer and the cover layer, which is removed before exposure.
  • This polymer layer enables a non-sticky negative overlay when exposing the printing plate and good contact between the image and the printing plate, since bubbles are avoided during the overlay. Examples of such protective layers can also be found, for example, in US Pat. No. 4,423,135 and DE-C 23 37 645.
  • EP-A 0 322 585 discloses printing plates made of a light-sensitive layer with special monomer mixtures which contain thermoplastic elastomeric block copolymers, preferably linear and radial block copolymers with polystyrene end blocks, which can also be oil-stretched, as binders. Polybutadiene and polyisoprene are preferably used as central blocks. The polystyrene content is usually 10-40%.
  • Such printing plates are, as is generally customary, exposed imagewise through a cover layer protecting the light-sensitive layer and the photo original, and the cover layer is removed after the exposure.
  • a preferred method for producing such multilayer, photopolymerizable printing plates is a process in which a previously extruded, photopolymerizable composition is introduced into the nip of a calender and calendered between a support and a cover element, thereby forming a photopolymerizable layer between them.
  • EP-B1 00 84 851 discloses a production process for a multilayer, photopolymerizable printing plate which has an elastomeric layer between the flexible, tear-resistant polymer layer and the photopolymerizable layer, which has an elastomeric binder, optionally a second binder, optionally a dye , possibly one or more monomers and possibly a photoinitiator.
  • EP-A 0 185 337 Such a production method is known from EP-A 0 185 337, in which at least the elastomeric layer of a multilayer cover element is also produced by extrusion and calendering.
  • the printing plates of EP-A 0 185 337 are also exposed imagewise, as is generally the case, through a polymeric protective layer.
  • a disadvantage of the photopolymerizable printing plates described is that the flexible, flexible polymer layer, which is required for the tack-free, bubble-free negative layer, complicates the development of the exposed plates. Due to their different solution behavior compared to the components of the photopolymerizable layer, either an additional development step, such as a prior removal of the polymer layer or a treatment with a special one Solvent, or the addition of additives to the actual developing solvent required. Some of these protective layers only swell in the development solvents and can only be removed by intensive mechanical treatment. In addition, each printing plate requires a polymeric protective layer which is specifically matched to its photopolymerizable layer, ie the composition of this polymer layer must be adapted to the respective photopolymerizable printing plate.
  • the present invention was therefore based on the object to eliminate the above problems and disadvantages and to provide a photopolymerizable printing plate, the surface of which is not sticky, so that a direct support of an original image on the printing plate is possible without damage or contamination of the original image .
  • good contact without bubbles between the original image and the printing plate must be ensured.
  • the printing plate should also be easier and cheaper to manufacture and process.
  • the usual washout development with common solvents should be possible without the addition of additives.
  • the ozone stability of the printing forms should also be increased.
  • other properties of the photopolymerizable printing plates should not be adversely affected, for example a reduction in photosensitivity should be avoided.
  • the Do not swell flexographic printing plates in the printing inks as this leads to an undesirable dot gain and thus to incorrect printing results.
  • a photopolymerizable printing plate consisting essentially of a) a support, b) a photopolymerizable layer containing at least one elastomeric binder, at least one ethylenically unsaturated monomer addition-polymerizable by actinic radiation and a photoinitiator or a photoinitiator system, c) one elastomeric layer containing at least one thermoplastic elastomeric block copolymer, and d) a cover film.
  • the elastomeric layer c) contains, as a binder, one or more thermoplastic elastomeric block copolymers which are composed of at least one polystyrene block and at least one polybutadiene, polyethylene and / or polypropylene block, the polystyrene content of the binder or of the binder mixture 10 to 35% by weight, the solution viscosity of the block copolymers for a 5.23% solution in toluene 5 5 mm 2 / s and the melt index measured according to ASTM D 1238 P ⁇ 10 g / 10 min.
  • the elastomeric layer c) contains, as a binder, one or more thermoplastic elastomeric block copolymers which are composed of at least one polystyrene block and at least one polybutadiene, polyethylene and / or polypropylene block, the polystyrene content of the binder or of the binder mixture 10 to 35% by weight, the solution viscosity
  • the printing plates according to the invention have good adhesion of the elastomeric layer to the photopolymerizable layer, so that there are no delamination problems.
  • the printing forms for the flexographic printing produced from the printing plates according to the invention show good printing properties which are comparable with the conventional printing forms.
  • the printing form surface is resistant to flexographic printing inks, even with long runs. No swelling of the surface was observed and the print quality was consistently good.
  • a particular advantage is that the printing plates according to the invention have good flexibility and that Surface is not brittle and does not tend to wrinkle even when the printing plates are subjected to high loads.
  • the use of only one development solvent makes it easier and safer to monitor the quality when washing out the exposed printing plate.
  • the washing-out speed can also be increased compared to conventional printing plates which are provided with a polyamide layer.
  • thermoplastic elastomeric block copolymers of the elastomeric layer c) which are essential to the invention are constructed from at least one polystyrene block and at least one polybutadiene, polyethylene and / or polypropylene block.
  • Polystyrene-polybutadiene or polystyrene-polybutadiene-polystyrene block copolymers are preferably used, in particular radial block copolymers, such as (polystyrene-polybutadiene) 4 -Si.
  • the polystyrene content of the binder or the binder mixture of the elastomeric layer c) is 10 to 35% by weight, preferably 15 to 30% by weight.
  • the block copolymers essential to the invention are also characterized by a solution viscosity (measured as a 5.23% solution in toluene) of ⁇ 5 mm 2 / s, in particular ⁇ 10 mm 2 / s, and by a melt index (measured according to ASTM D 1238 P (5th kg / 190 ° C) of ⁇ 10 g / 10 min, in particular ⁇ 2 g / 10 min.
  • Radial (polystyrene-polybutadiene) 4 -Si block copolymers with a polystyrene content of 18 to 23% by weight, a solution viscosity of ⁇ 15 mm 2 / s and a melt index of ⁇ 1.5 g are particularly preferred as binders of the elastomeric layer c) / min used.
  • the content of this polymer in the elastomeric layer c) is preferably between 1.5: 1 to 1: 1.5. However, 1: 1 mixtures are particularly preferably used.
  • Examples of such polymers are copolymers of acrylonitrile, butadiene and methyl methacrylate or those which additionally contain styrene.
  • the acrylonitrile content should be between 5 to 35% by weight, preferably between 5 to 20% by weight.
  • a methyl methacrylate / acrylonitrile / butadiene / styrene tetrapolymer (46/9/14/31) with a haze of 10% and a Rockwell hardness of 103 is particularly suitable.
  • the elastomeric layer can contain 5-30% by weight, preferably 15-25% by weight, of a polymer with the following structural unit A are added, wherein R 1 for H and CH 3 , R 2 and R 3 independently of one another are H and substituted or unsubstituted alkyl or aryl groups and R 4 and R 5 independently of one another are H and substituted or unsubstituted alkyl groups and m and n Can assume values from 0 to 10, the sum of m and n being equal to 2 to 20.
  • the elastomeric layer c) should have a thickness of 0.01 to 0.5 mm, preferably 0.025 to 0.12 mm.
  • the layer can be applied by casting from solvents such as toluene, acetone, methylene chloride, perchlorethylene, methyl ethyl ketone, methyl isobutyl ketone or mixtures etc. or by extrusion coating directly onto the cover sheet d), e.g. a polyethylene terephthalate film can be applied.
  • solvents such as toluene, acetone, methylene chloride, perchlorethylene, methyl ethyl ketone, methyl isobutyl ketone or mixtures etc.
  • solvents such as toluene, acetone, methylene chloride, perchlorethylene, methyl ethyl ketone, methyl isobutyl ketone or mixtures etc.
  • solvents such as toluene, acetone, methylene chloride, perchlorethylene, methyl ethyl ketone, methyl isobutyl ketone or mixtures etc.
  • the photopolymerizable layer b) of the printing plates according to the invention contains at least one elastomeric binder.
  • Block copolymers of the ABA type which have an elastomeric block, for example polybutadiene or polyisoprene, between two thermoplastic blocks, for example polystyrene, are preferred.
  • Linear and radial block copolymers with polystyrene end blocks are particularly preferably used, such as, for example, polystyrene-polyisoprene-polystyrene, (polystyrene-polybutadiene) 4 -Si or (polystyrene-polyisoprene) 4 -Si.
  • the average molecular weight of the block copolymers should be between 80,000 and 300,000, preferably between 100,000 and 250,000.
  • the proportion of polystyrene should be 10 to 40% by weight, preferably 15 to 30% by weight.
  • the photopolymerizable layer b) also contains at least one ethylenically unsaturated monomer which is addition-polymerizable by actinic radiation.
  • monomers with one ethylenically unsaturated group can be both monomers with one ethylenically unsaturated group and those with several ethylenically unsaturated groups.
  • the monomers can be used alone or in combination with one another.
  • Monomer mixtures of monounsaturated acrylates and / or methacrylates and polyunsaturated acrylates and / or methacrylates are preferably used. Such monomer mixtures are described in DE-C1 37 44 243.
  • the photopolymerizable layer b) contains a photoinitiator or a photoinitiator system, for example: ⁇ -methylbenzoin, benzophenone, benzil-dimethyl-ketal or ethylanthraquinone / 4,4'-bis (dimethylamino) benzophenone.
  • the photopolymerizable layer b) may contain further additives, such as, for example, fillers, dyes, antioxidants and plasticizers as mentioned in EP-B1 00 84 851. 0-30% by weight of plasticizer, for example based on polystyrene or polybutadiene and with an average molecular weight of between 1,000 and 10,000, is preferably used.
  • the photopolymerizable layer b) generally contains 65-95% by weight of binder, 5-30% by weight of monomer or monomer mixture and 0.5-5% by weight of initiator.
  • Suitable layer supports a) are, for example Aluminum, steel or plastic films. Polyester films are preferred, which can optionally be provided with an adhesive layer and / or antihalation layer. Polyethylene terephthalate films are particularly suitable.
  • the photopolymerizable printing plates according to the invention are preferably produced by the process described in EP-B1 00 84 851.
  • a previously extruded photopolymerizable mass is placed in the nip of a calender introduced and calendered between a support and a cover element, consisting of a cover film d) and the layer c) according to the invention, whereby a photopolymerizable layer is formed which on one side to the support and on the other side to the elastomeric layer c) of Cover elements adjoining.
  • the photopolymerizable printing plate produced in this way is cooled and, if necessary, subjected to pre-exposure with actinic radiation through the layer support. Then the cover film is usually removed, an image-bearing transparency is placed on the photopolymerizable printing plate and exposed to actinic radiation.
  • the uncrosslinked areas of the photopolymerizable layer b) and the elastomeric layer c) are then removed by washing with a developer solvent.
  • Organic solvents such as chlorinated hydrocarbons, e.g. 1,1,1-trichloroethane, or saturated or aromatic hydrocarbons.
  • the solvents of German patent application P 38 28 551.7 are preferably used.
  • the solvent can be applied in any manner for development, e.g.
  • the printing forms thus obtained have been dried at 40 to 75 ° C., they can be exposed in any order and / or to produce a tack-free surface, e.g. be treated with a solution containing free halogen.
  • the dye and the tetrapolymer were kneaded together at 116 ° C. and then extruded and granulated.
  • This mixture and the other ingredients of the elastomeric layer c) were then processed to a 15% solution in methylene chloride.
  • This casting solution was applied by means of an extrusion slot caster with a gap width of 0.38 mm to an uncoated polyethylene terephthalate base, as described in EP-B1 00 84 851 example 1, dried and provided with a silicone-coated polyethylene terephthalate protective layer.
  • the dry layer thickness was 0.051 mm.
  • Example 1 A 17% solution in methylene chloride was processed as in Example 1 to give the elastomeric layer c).
  • the printing plate thus produced was produced and further processed as described in Example 1.
  • the photosensitivity, the exposure latitude and the development behavior corresponded to printing plates according to the prior art.
  • the printing plate was characterized by improved ozone stability.
  • the surface of the photopolymerizable printing plate was not sticky, so that the exposure original could be removed without problems after the exposure. It was completely undamaged and clean and suitable for reuse.
  • the surface of the flexographic printing plate thus produced was completely intact, showed no wrinkling and no swelling with the printing inks used.
  • the tetrapolymer was dissolved in toluene / methyl ethyl ketone (4: 1) and the solution was filtered. A 20% casting solution was prepared from this solution and the other components.
  • the production of the elastomeric layer and all further processing steps were carried out as in Example 2.
  • the photosensitivity, the exposure latitude and the development behavior corresponded to printing plates according to the prior art.
  • the printing plate was distinguished by improved ozone stability.
  • the surface of the photopolymerizable printing plate was not sticky, so that the exposure original could be removed without problems after the exposure. It was completely undamaged and clean and suitable for reuse.
  • the surface of the flexographic printing plate thus produced was completely intact, showed no wrinkling and no swelling with the printing inks used.
  • Example 2 The casting solution and the elastomeric layer and all further processing steps were carried out as in Example 2.
  • the photosensitivity, the exposure latitude and the development behavior corresponded to printing plates according to the prior art.
  • the printing plate was characterized by improved ozone stability.
  • the surface of the photopolymerizable printing plate was not sticky, so that the exposure original could be removed without problems after the exposure. It was completely undamaged and clean and suitable for reuse.
  • the surface of the flexographic printing plate thus produced was completely intact, showed no wrinkling and no swelling with the printing inks used.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)

Claims (8)

  1. Cliché photopolymérisable constitué essentiellement de :
    a) d'un porteur de couche,
    b) une couche photopolymérisable contenant au moins un liant élastomère, au moins un monomère éthyléniquement insaturé susceptible de polymériser addition sous l'action d'un rayonnement actinique et un photoinitiateur ou système photoinitiateur;
    c) une couche élastomère contenant au moins un copolymère en bloc élastomère thermoplastique ; et
    d) un film de recouvrement,
    caractérisé en ce que la couche élastomère c) contient en tant que liant un ou plusieurs copolymères séquencés élastomères thermoplastiques, constitués à partir d'au moins un bloc polystyrène et au moins un bloc polybutadiène-polyéthylène et/ou polypropylène, et dans lequel la teneur en polystyrène du liant ou du mélange de liant est de 10 à 35 % en poids, la viscosité en solution des copolymères séquencés d'une solution à 5,23 % dans du toluène est ≥ à 5 mm2/s et l'indice de fusion mesuré selon ASTM D 1238 P est ≤ 10 g/10 minutes.
  2. Cliché photopolymérisable selon la revendication 1, caractérisé en ce qu'il contient un copolymère séquencé polystyrène-polybutadiène ou polystyrène-polybutadiène-polystyrène ayant une teneur en polystyrène de 15 à 30 % en poids, une viscosité en solution ≥ à 10 mm2/s et un indice de fusion ≤ 2 g/10 minutes.
  3. Cliché photopolymérisable selon la revendication 1 ou 2, caractérisé en ce que la couche élastomère c) contient un copolymère séquencé radial (polystyrène-polybutadiène)4-Si ayant une teneur en polystyrène de 18 à 23 % en poids. une viscosité en solution ≥ à 15 mm2/s et un indice de fusion ≤ 1,5 g/10 minutes.
  4. Cliché photopolymérisable selon les revendications 1 à 3, caractérisé en ce que la couche élastomère c) contient 30 à 70 % en poids d'un polymère ayant une turbidité mesurée selon ASTM D 1009 ≤20 % et une dureté Rockwell mesurée selon ASTM D 785 ≥ à 50
  5. Cliché photopolymérisable selon les revendications 1 à 4, caractérisé en ce que la couche élastomère c) contient 40 à 60 % en poids d'un polymère ayant une turbidité mesurée selon ASTM D 1009 ≤ 12 % et une dureté Rockwell mesurée selon ASTM D 785 ≥ à 80
  6. Procédé de fabrication d'une couche élastomère c) d'un cliché polymérisable selon la revendication 4 ou 5, caractérisé en ce que le polymère selon la revendication 4 ou 5 est dissout dans le solvant pour la solution de coulée et que cette solution est filtrée, et qu'ensuite la solution de coulée pour la couche élastomère c) est fabriquée à partir des autres composants et de la solution du polymère ainsi prétraité.
  7. Procédé de fabrication de cliché photopolymérisable dans lequel une masse photopolymérisable d'au moins un monomère éthyléniquement insaturé. susceptible de polymériser par addition sous l'action d'un rayonnement et un photoinitiateur ou un système de photoinitiateur, est introduite dans la fente d'une calandre et est calandrée entre un support a) et un élément de recouvrement multicouches, et dans lequel la couche photopolymérisable b) est formée entre eux. et dans lequel procédé l'élément de recouvrement multicouches est constitué d'une couche élastomère c) contenant au moins un copolymères séquencé,
    caractérisé en ce que la couche élastomère c) contient en tant que liant un ou plusieurs copolymères séquencés élastomères thermoplastiques, qui sont constitués d'au moins un bloc polystyrène et d'au moins un bloc polybutadiène, polyéthylène et/ou polypropylène, et en ce que la teneur en polystyrène du liant ou du mélange de liant est de 10 à 35 % en poids, la viscosité de la solution des copolymères séquencés d'une solution à 5,23 % dans du toluène est ≥ à 5 mm2/s et l'indice de fusion mesuré selon ASTM D 1238 P est ≤ 10 g/10 minutes.
  8. Procédé de fabrication de formes d'impression flexographiques comprenant :
    1) l'exposition, à la façon dont on forme une image d'un cliché photopolymérisable selon les revendications 1 à 5 à travers la couche élastomère c) :
    2) l'élimination des zones non exposées de la couche photopolymérisable b) et de la couche élastomère c) par lavage avec des solvants de développement.
EP91110805A 1990-07-19 1991-06-29 Cliché photopolymérisable pour l'impression flexographique Expired - Lifetime EP0467136B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4022978 1990-07-19
DE4022978A DE4022978C1 (fr) 1990-07-19 1990-07-19

Publications (2)

Publication Number Publication Date
EP0467136A1 EP0467136A1 (fr) 1992-01-22
EP0467136B1 true EP0467136B1 (fr) 1997-12-17

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EP91110805A Expired - Lifetime EP0467136B1 (fr) 1990-07-19 1991-06-29 Cliché photopolymérisable pour l'impression flexographique

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EP (1) EP0467136B1 (fr)
JP (1) JP2607775B2 (fr)
CA (1) CA2047302A1 (fr)
DE (2) DE4022978C1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1031303A (ja) * 1994-09-29 1998-02-03 Nippon Zeon Co Ltd 感光性組成物及び感光性ゴム版
DE19703917A1 (de) * 1997-02-03 1998-08-06 Du Pont Deutschland Flexographische Druckformen für den Wellpappendruck
DE19859623A1 (de) 1998-12-23 2000-08-24 Basf Drucksysteme Gmbh Photopolymerisierbare Druckformen mit Oberschicht zur Herstellung von Reliefdruckformen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2215090C3 (de) * 1971-04-01 1981-02-12 E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) Fotopolymerisierbares Aufzeichnungsmaterial

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427759A (en) * 1982-01-21 1984-01-24 E. I. Du Pont De Nemours And Company Process for preparing an overcoated photopolymer printing plate
JPS60181740A (ja) * 1984-02-28 1985-09-17 Asahi Chem Ind Co Ltd フレキソ印刷版用感光性エラストマ−組成物
US4622088A (en) * 1984-12-18 1986-11-11 E. I. Du Pont De Nemours And Company Process for preparing photopolymer flexographic element with melt extrusion coated elastomeric surface layer
DE3744243C2 (de) * 1987-12-24 1995-12-07 Du Pont Deutschland Verbesserte photopolymerisierbare Aufzeichnungsmaterialien

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2215090C3 (de) * 1971-04-01 1981-02-12 E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) Fotopolymerisierbares Aufzeichnungsmaterial

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Publication number Publication date
DE59108907D1 (de) 1998-01-29
JPH04271351A (ja) 1992-09-28
CA2047302A1 (fr) 1992-01-20
JP2607775B2 (ja) 1997-05-07
EP0467136A1 (fr) 1992-01-22
DE4022978C1 (fr) 1991-08-08

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